CN103450610A - Gel polymer electrolyte membrane, and preparation method and application thereof - Google Patents
Gel polymer electrolyte membrane, and preparation method and application thereof Download PDFInfo
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- CN103450610A CN103450610A CN 201210175304 CN201210175304A CN103450610A CN 103450610 A CN103450610 A CN 103450610A CN 201210175304 CN201210175304 CN 201210175304 CN 201210175304 A CN201210175304 A CN 201210175304A CN 103450610 A CN103450610 A CN 103450610A
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- CFCOGOZCDDTVFQ-UHFFFAOYSA-N C[N]1(COCCOC)CCCC1 Chemical compound C[N]1(COCCOC)CCCC1 CFCOGOZCDDTVFQ-UHFFFAOYSA-N 0.000 description 3
- 0 C*1(COCCOC)CCCC1 Chemical compound C*1(COCCOC)CCCC1 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/13—Energy storage using capacitors
Abstract
The embodiment of the invention discloses a gel polymer electrolyte membrane. The material of the gel polymer electrolyte membrane contains a mixed material formed by mixing a polymer substrate material and an ionic liquid, wherein the mass ratio of the polymer substrate material to the ionic liquid is 100:30-50, the polymer substrate material is polyvinyl alcohol, and the ionic liquid is an N-methylpyrrolidines ionic liquid. In addition, the embodiment of the invention also discloses a preparation method and an application of the gel polymer electrolyte membrane. The gel polymer electrolyte membrane and the preparation method thereof provided by the invention have the characteristics of being high in safety performance, friendly to environment, and conducive to large-scale preparation and the like.
Description
Technical field
The present invention relates to the electrochemical device association area, relate in particular to a kind of gel polymer electrolyte film and its production and use.
Background technology
Ultracapacitor is a kind of novel energy device between rechargeable battery and electrical condenser, have that volume is little, capacity is large, charge velocities is fast, have extended cycle life, the advantage such as discharging efficiency is high, operating temperature range is wide, good reliability and contaminant-free maintenance-free, be a kind of novel, efficient, practical energy accumulating device, thereby be widely used in AC-battery power source of military field, device for mobile communication, computer and electromobile etc.
The ultracapacitor working electrolyte is divided into aqueous electrolyte, organic liquid electrolytic solution and polymer dielectric.The decomposition voltage of aqueous electrolyte is low, thereby studies less.The advantage of now widely used liquid electrolyte is that specific conductivity is high, but inflammable owing to containing, volatile organic solvent, it discharges inflammable gas in charge and discharge process, particularly under some unconventional working conditions, (as high-power, discharge and recharge, super-charge super-discharge etc.) produces the generation that gas is accelerated in large calorimetric meeting, cause inner pressure of battery to increase, gas leakage, blast even on fire, thereby have serious potential safety hazard.The studied persons of advantage such as polymer dielectric ultracapacitor and polymer electrolyte lithium-ion battery are safe because having, nothing is leaked, leakage current is little pay attention to.But under the solid polymer electrolyte room temperature, specific conductivity is lower by (10
-5~ 10
-4s/cm), use application to be restricted, thereby gel polymer electrolyte become research emphasis.
Summary of the invention
Given this, the embodiment of the present invention aims to provide a kind of gel polymer electrolyte film and preparation method thereof, has that safety performance is high, environmental friendliness, is conducive to the characteristics such as extensive preparation, can be for the preparation of ultracapacitor.
The embodiment of the present invention provides a kind of gel polymer electrolyte film, the material of described gel polymer electrolyte film comprises the mixing material that polymer-based carbon bottom material and ionic liquid are mixed to form, the mass ratio of described polymer-based carbon bottom material and described ionic liquid is 100:30 ~ 50, described polymer-based carbon bottom material is polyvinyl alcohol, and described ionic liquid is for having the compound as shown in structural formula (1):
In formula, Y
-for BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -.
Preferably, the matter average molecular weight of polyvinyl alcohol (PVA) is 2 ~ 200,000.
Correspondingly, the embodiment of the present invention also provides a kind of preparation method of gel polymer electrolyte film, comprises the following steps:
(1) ratio that is 1: 1.05 ~ 1.2 with the methoxy ethoxy methyl halide according to mol ratio by the N-crassitude is mixed, and is heated to 60 ℃ ~ 80 ℃ under protection of inert gas, and stirring reaction 48 ~ 72 hours obtains having the compd A that following structural formula means:
In formula, X
-for Cl
-, Br
-, I
-;
(2) by described compd A and general formula, be M
+y
-salt according to mol ratio, be 1:1 ~ 1.1 ratio is mixed, add deionized water, at room temperature stirring reaction is 8 ~ 24 hours, obtains having the ionic liquid meaned as structural formula (1):
Wherein, M
+for Na
+, K
+or NH
4 +; Y
-for BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -;
(3) by described ionic liquid, with polyvinyl alcohol, according to mass ratio, be that 30 ~ 50:100 mixes; add organic solvent; under anhydrous and protection of inert gas; be heated to 40 ℃ ~ 60 ℃; the formation viscous solution that stirs, cast in described viscous solution on sheet glass, 80 ℃ ~ 100 ℃ lower vacuum-dryings 24 hours ~ 48 hours; after cooling, peel off and obtain described gel polymer electrolyte film.
Step (1) is for making the N-crassitude react and make compd A with the methoxy ethoxy methyl halide, and reaction formula is as follows:
Wherein, RX is the methoxy ethoxy methyl halide.
Preferably, the methoxy ethoxy methyl halide is methoxy ethoxy methyl chloride, methoxy ethoxy monobromethane or methoxy ethoxy methyl iodide.
Wherein, the structural formula of methoxy ethoxy methyl chloride, methoxy ethoxy monobromethane or methoxy ethoxy methyl iodide is respectively:
Preferably, described rare gas element is nitrogen (N
2) or argon gas (Ar
2).
Preferably, step (1) also comprises the following purification process to compd A: after completion of the reaction, that the reaction solution of described reaction is standing cooling, use the ethyl acetate washed product, and, 80 ℃ ~ 100 ℃ lower vacuum-dryings 24 hours ~ 48 hours, obtain the compd A of purifying.
Step (2) is M for making compd A and general formula
+y
-reactant salt make ionic liquid, reaction formula is as follows:
In formula, M
+for Na
+, K
+or NH
4 +; Y
-for BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -.
Preferably, step (2) also comprises the following purification process to described ionic liquid: after completion of the reaction, with methylene dichloride or chloroform extraction reaction solution 1 ~ 5 time, collect extraction liquid, strip to using saturated AgNO with deionized water
3aqueous solution titration water by after the organic phase evaporation concentration, and, 80 ℃ ~ 100 ℃ lower vacuum-dryings 24 hours ~ 48 hours, obtains the described ionic liquid of purifying till producing without precipitation.
Ionic liquid has the characteristics such as specific conductivity high (about 5ms/cm), fusing point low (30 ℃ of left and right), electrochemical window wide (5V left and right), has the advantages such as non-volatile, non-combustible, Heat stability is good with respect to inflammable, volatile, shortcoming, the ionic liquid such as thermostability is bad of organic liquid.Therefore, in gel polymer electrolyte, mixed ionic liquid can reduce the usage quantity of organic liquid, has reduced electrolytical inflammableness and volatility, not only improves the security of gel polymer electrolyte film, stability, and environmental friendliness.
Step (3) is for making N-crassitude ionic liquid/polyvinyl alcohol (PVA) gel polymer electrolyte film.
Preferably, the matter average molecular weight of polyvinyl alcohol (PVA) is 2 ~ 200,000.
Preferably, organic solvent is acetonitrile, ethanol or tetrahydrofuran (THF) (THF).
Preferably, the mass ratio of organic solvent and polyvinyl alcohol is 20% ~ 30%.
In addition, the embodiment of the present invention also provides the purposes of gel polymer electrolyte film in ultracapacitor.
Particularly, gel polymer electrolyte film is assembled into to ultracapacitor: by Graphene, (specific surface area is about 700m
2/ g), acetylene black and PVDF are Graphene according to mass ratio: the ratio of acetylene black: PVDF=85 ~ 90:3 ~ 7:3 ~ 10 is mixed, and Graphene: NMP=1:2 ~ 20 add NMP in mass ratio, fully stirs and makes it to become the slurry mixed; Then by the slurry blade coating on the aluminium foil cleaned through ethanol, under the vacuum of 0.01MPa, 100 ℃ are dried to constant weight, and are pressed into Graphene electrodes in 10 ~ 15MPa pressure lower roll, and are cut into the electrode disk; The gel polymer electrolyte prepared is placed between two Graphene electrodes, and on stamping machine, the button electrical condenser is made in sealing.
Implement the embodiment of the present invention, there is following beneficial effect:
(1) gel polymer electrolyte film safety performance provided by the invention is high, stability is high and environmental friendliness, is applicable to the electrochemical devices such as ultracapacitor;
(2) preparation method of gel polymer electrolyte film provided by the invention is easy and simple to handle, is conducive to realize large-scale production.
The accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, below will the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is preparation method's schematic flow sheet of gel polymer electrolyte film provided by the invention;
Fig. 2 is the constant current charge-discharge curve of the ultracapacitor of the embodiment of the present invention 1.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making under the creative work prerequisite the every other embodiment obtained, belong to the scope of protection of the invention.
Embodiment 1
A kind of preparation method of gel polymer electrolyte film, comprise the steps:
(1) prepare chlorination N-methoxy ethoxy methyl-N-crassitude
Add respectively (85g, 1mol) N-crassitude and (148.8g, 1.2mol) methoxy ethoxy methyl chloride in the flask of 250mL, after mixing, at N
2under protection, be heated to 60 ℃, stirring reaction 72h, after completion of the reaction, the standing room temperature that is cooled to, use ethyl acetate washed product 3 times, and at 80 ℃ of lower vacuum-drying 48h, obtain lurid solid, be chlorination N-methoxy ethoxy methyl-N-crassitude, yield is 83%;
(2) prepare N-methoxy ethoxy methyl-N-crassitude tetrafluoroborate ion liquid
By the above-mentioned chlorination N-methoxy ethoxy methyl made-N-crassitude (102.5g, 0.5mol) and NaBF
4(58.3g, 0.53mol) is dissolved in the 100mL deionized water, stirring reaction 8h at room temperature, after completion of the reaction, by 250mL dichloromethane extraction 3 times for reaction solution, combining extraction liquid; Then at every turn with 60mL deionized water back extraction until with saturated AgNO
3till aqueous solution titration water produces without precipitation, after methylene dichloride is concentrated with Rotary Evaporators, at 80 ℃ of vacuum-drying 48h, obtain colourless liquid, be N-methoxy ethoxy methyl-N-crassitude tetrafluoroborate ion liquid.
N-methoxy ethoxy methyl-N-crassitude tetrafluoroborate ion liquid building-up reactions formula is as follows:
The nuclear magnetic resonance spectrum diagram data of chlorination N-methoxy ethoxy methyl-N-crassitude a tetrafluoro borate is as follows:
1H?NMR(CDCl
3,400MHz,ppm):6.71(d,2H),6.45(t,2H),5.92(s,2H),3.84(m,2H),3.57(s,3H),3.38(m,2H),3.24(s,3H)。
(3) prepare N-methoxy ethoxy methyl-N-crassitude tetrafluoroborate ion liquid/polyvinyl alcohol gel polymer dielectric film:
Add successively 100g polyvinyl alcohol (matter average molecular weight 100,000), 40gN-methoxy ethoxy methyl-N-crassitude a tetrafluoro borate and 25g AN(acetonitrile in the there-necked flask of 500mL).At dry rare gas element N
2protection under, be heated to 40 ℃, and stir and to allow polyvinyl alcohol dissolve, make system become even viscous solution.The viscous solution that gained is mixed casts on clean sheet glass, is transferred to rapidly in vacuum drying oven, and under 80 ℃, dry 48h, slough solvent.After being cooled to room temperature, separating elastica transparent on sheet glass and be N-methoxy ethoxy methyl-N-crassitude tetrafluoroborate ion liquid/polyvinyl alcohol gel polymer dielectric film in glove box.
The N-methoxy ethoxy methyl that makes-N-crassitude tetrafluoroborate ion liquid/polyvinyl alcohol gel polymer dielectric film is assembled into to ultracapacitor: (specific surface area is about 700m to take the 9g Graphene
2/ g), 0.5g acetylene black and 0.5g PVDF, and add 80g NMP, fully stir and make it to become the slurry mixed.Then by its blade coating on the aluminium foil cleaned through ethanol, under the vacuum of 0.01MPa, 100 ℃ are dried to constant weight, and are pressed into Graphene electrodes in 10MPa pressure lower roll, and are cut into the electrode disk.The above-mentioned N-methoxy ethoxy methyl prepared-N-crassitude tetrafluoroborate ion liquid/polyvinyl alcohol gel polymer dielectric film is placed between two Graphene electrodes, and on stamping machine, the button electrical condenser is made in sealing.
Utilize the charge-discharge test instrument to carry out the constant current charge-discharge test to the ultracapacitor assembled in the present embodiment, in the electrochemical window of 0 ~ 2.7V, with the electric current of 0.5A/g, record its charging and discharging curve as shown in Figure 2.
As can be seen from Figure 2, the prepared gel polymer electrolyte of the embodiment of the present invention is suitable for the electrolytic solution of ultracapacitor, and has stability preferably in the electrochemical window of 0 ~ 2.7V.
Embodiment 2
A kind of preparation method of gel polymer electrolyte film, comprise the steps:
(1) prepare bromination N-methoxy ethoxy methyl-N-crassitude
Add respectively (85g, 1mol) N-crassitude and (136.4g, 1.1mol) methoxy ethoxy monobromethane in the flask of 250mL, after mixing, at N
2under protection, be heated to 70 ℃, stirring reaction 60h, after completion of the reaction, the standing room temperature that is cooled to, use ethyl acetate washed product 3 times, and at 90 ℃ of lower vacuum-drying 36h, obtain lurid solid, be bromination N-methoxy ethoxy methyl-N-crassitude, yield is 87%;
(2) prepare N-methoxy ethoxy methyl-N-crassitude hexafluorophosphate ionic liquid
By the above-mentioned bromination N-methoxy ethoxy methyl made-N-crassitude (102.5g, 0.5mol) and KPF
6(101.2g, 0.55mol) is dissolved in the 100mL deionized water, stirring reaction 16h at room temperature, after completion of the reaction, by 250mL dichloromethane extraction 3 times for reaction solution, combining extraction liquid; Then at every turn with 60mL deionized water back extraction until with saturated AgNO
3till aqueous solution titration water produces without precipitation, after methylene dichloride is concentrated with Rotary Evaporators, at 90 ℃ of vacuum-drying 36h, obtain colourless liquid, be bromination N-methoxy ethoxy methyl-N-crassitude hexafluorophosphate ionic liquid.
N-methoxy ethoxy methyl-N-crassitude hexafluorophosphate ionic liquid building-up reactions formula is as follows:
The nuclear magnetic resonance spectrum diagram data of N-methoxy ethoxy methyl-N-crassitude hexafluorophosphate is as follows:
1H?NMR(CDCl
3,400MHz,ppm):6.73(d,2H),6.46(t,2H),5.93(s,2H),3.86(m,2H),3.58(s,3H),3.39(m,2H),3.25(s,3H)。
(3) prepare N-methoxy ethoxy methyl-N-crassitude hexafluorophosphate ionic liquid/polyvinyl alcohol gel polymer dielectric film:
Add successively 100g polyvinyl alcohol (matter average molecular weight 20,000), 30g bromination N-methoxy ethoxy methyl-N-crassitude hexafluorophosphate and 30g EtOH(ethanol in the there-necked flask of 500mL).At dry rare gas element N
2protection under, be heated to 50 ℃, and stir and to allow polyvinyl alcohol dissolve, make system become even viscous solution.The viscous solution that gained is mixed casts on clean sheet glass, is transferred to rapidly in vacuum drying oven, and under 90 ℃, dry 36h, slough solvent.After being cooled to room temperature, separating elastica transparent on sheet glass and be N-methoxy ethoxy methyl-N-crassitude hexafluorophosphate ionic liquid/polyvinyl alcohol gel polymer dielectric film in glove box.
The N-methoxy ethoxy methyl that makes-N-crassitude hexafluorophosphate ionic liquid/polyvinyl alcohol gel polymer dielectric film is assembled into to ultracapacitor: (specific surface area is about 700m to take the 8.5g Graphene
2/ g), 0.7g acetylene black and 1.0g PVDF, and add 60g NMP, fully stir and make it to become the slurry mixed.Then by its blade coating on the aluminium foil cleaned through ethanol, under the vacuum of 0.01MPa, 100 ℃ are dried to constant weight, and are pressed into Graphene electrodes in 15MPa pressure lower roll, and are cut into the electrode disk.The above-mentioned N-methoxy ethoxy methyl prepared-N-crassitude hexafluorophosphate ionic liquid/polyvinyl alcohol gel polymer dielectric film is placed between two Graphene electrodes, and on stamping machine, the button electrical condenser is made in sealing.
Utilize the charge-discharge test instrument to carry out the constant current charge-discharge test to the ultracapacitor assembled in the present embodiment, there is stability preferably in the electrochemical window of 0 ~ 2.7V.
Embodiment 3
A kind of preparation method of gel polymer electrolyte film, comprise the steps:
(1) prepare iodate N-methoxy ethoxy methyl-N-crassitude
Add respectively (85g, 1mol) N-crassitude and (226.8g, 1.05mol) methoxy ethoxy methyl iodide in the flask of 250mL, after mixing, at N
2under protection, be heated to 80 ℃, stirring reaction 48h, after completion of the reaction, the standing room temperature that is cooled to, use ethyl acetate washed product 3 times, and at 100 ℃ of lower vacuum-drying 24h, obtain lurid solid, be iodate N-methoxy ethoxy methyl-N-crassitude, yield is 87%;
(2) prepare two (fluoroform sulphonyl) the inferior amine salt ionic liquids of N-methoxy ethoxy methyl-N-crassitude
By the above-mentioned iodate N-methoxy ethoxy methyl made-N-crassitude (102.5g, 0.5mol) and fluoroform sulfimide potassium TFSI-K (159.5g, 0.5mol) be dissolved in the 100mL deionized water, stirring reaction 24h at room temperature, after completion of the reaction, by reaction solution 250mL dichloromethane extraction 3 times, combining extraction liquid; Then at every turn with 60mL deionized water back extraction until with saturated AgNO
3till aqueous solution titration water produces without precipitation, after methylene dichloride is concentrated with Rotary Evaporators, at 100 ℃ of vacuum-drying 24h, obtain colourless liquid, be two (fluoroform sulphonyl) the inferior amine salt ionic liquids of N-methoxy ethoxy methyl-N-crassitude.
Two (fluoroform sulphonyl) the inferior amine salt ionic liquid building-up reactions formulas of N-methoxy ethoxy methyl-N-crassitude are as follows:
The nuclear magnetic resonance spectrum diagram data of two (fluoroform sulphonyl) inferior amine salts of N-methoxy ethoxy methyl-N-crassitude is as follows:
1h NMR (CDCl
3, 400MHz, ppm): 6.74 (d, 2H), 6.47 (t, 2H), 5.95 (s, 2H), 3.87 (m, 2H), 3.59 (s, 3H), 3.40 (m, 2H), 3.27 (s, 3H).
(3) prepare two (fluoroform sulphonyl) inferior amine salt ionic liquids of N-methoxy ethoxy methyl-N-crassitude/polyvinyl alcohol gel polymer dielectric film:
Add successively 100g polyvinyl alcohol (matter average molecular weight 200,000), two (fluoroform sulphonyl) inferior amine salts of 50gN-methoxy ethoxy methyl-N-crassitude and 20g THF(tetrahydrofuran (THF) in the there-necked flask of 500mL).At dry rare gas element N
2protection under, be heated to 60 ℃, and stir and to allow polyvinyl alcohol dissolve, make system become even viscous solution.The viscous solution that gained is mixed casts on clean sheet glass, is transferred to rapidly in vacuum drying oven, and under 100 ℃, dry 24h, slough solvent.After being cooled to room temperature, separating elastica transparent on sheet glass and be two (fluoroform sulphonyl) inferior amine salt ionic liquids of N-methoxy ethoxy methyl-N-crassitude/polyvinyl alcohol gel polymer dielectric film in glove box.
Two (fluoroform sulphonyl) inferior amine salt ionic liquids of the N-methoxy ethoxy methyl that makes-N-crassitude/polyvinyl alcohol gel polymer dielectric film is assembled into to ultracapacitor: (specific surface area is about 700m to take the 8.7g Graphene
2/ g), 0.5g acetylene black and 0.7g PVDF, and add 60g NMP, fully stir and make it to become the slurry mixed.Then by its blade coating on the aluminium foil cleaned through ethanol, under the vacuum of 0.01MPa, 100 ℃ are dried to constant weight, and are pressed into Graphene electrodes in 15MPa pressure lower roll, and are cut into the electrode disk.Two (fluoroform sulphonyl) inferior amine salt ionic liquids of the above-mentioned N-methoxy ethoxy methyl prepared-N-crassitude/polyvinyl alcohol gel polymer dielectric film is placed between two Graphene electrodes, and on stamping machine, the button electrical condenser is made in sealing.
Utilize the charge-discharge test instrument to carry out the constant current charge-discharge test to the ultracapacitor assembled in the present embodiment, there is stability preferably in the electrochemical window of 0 ~ 2.7V.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.
Claims (10)
1. a gel polymer electrolyte film, it is characterized in that, the material of described gel polymer electrolyte film comprises the mixing material that polymer-based carbon bottom material and ionic liquid are mixed to form, the mass ratio of described polymer-based carbon bottom material and described ionic liquid is 100:30 ~ 50, described polymer-based carbon bottom material is polyvinyl alcohol, and described ionic liquid is for having the compound as shown in structural formula (1):
Y in formula
-for BF
4 -, PF
6 -, (CF
3sO
2)
2n-or CF
3sO
3 -.
2. gel polymer electrolyte film as claimed in claim 1, is characterized in that, the matter average molecular weight of described polyvinyl alcohol is 2 ~ 200,000.
3. the preparation method of a gel polymer electrolyte film, is characterized in that, comprises the following steps:
(1) ratio that is 1: 1.05 ~ 1.2 with the methoxy ethoxy methyl halide according to mol ratio by the N-crassitude is mixed, and is heated to 60 ℃ ~ 80 ℃ under protection of inert gas, and stirring reaction 48 ~ 72 hours obtains having the compd A that following structural formula means:
In formula, X
-for Cl
-, Br
-, I
-;
(2) by described compd A and general formula, be M
+y
-salt according to mol ratio, be 1:1 ~ 1.1 ratio is mixed, add deionized water, at room temperature stirring reaction is 8 ~ 24 hours, obtains having the ionic liquid meaned as structural formula (1):
Wherein, M
+for Na
+, K
+or NH
4 +; Y
-for BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -;
(3) ratio that is 30 ~ 50:100 with polyvinyl alcohol according to mass ratio by described ionic liquid is mixed; add organic solvent; under anhydrous and protection of inert gas; be heated to 40 ℃ ~ 60 ℃; the formation viscous solution that stirs, cast in described viscous solution on sheet glass, 80 ℃ ~ 100 ℃ lower vacuum-dryings 24 hours ~ 48 hours; after cooling, peel off and obtain described gel polymer electrolyte film.
4. the preparation method of gel polymer electrolyte film as claimed in claim 3, is characterized in that, methoxy ethoxy methyl halide described in step (1) is methoxy ethoxy methyl chloride, methoxy ethoxy monobromethane or methoxy ethoxy methyl iodide.
5. the preparation method of gel polymer electrolyte film as claimed in claim 3, is characterized in that, described rare gas element is nitrogen or argon gas.
6. the preparation method of gel polymer electrolyte film as claimed in claim 3, it is characterized in that, step (1) also comprises the following purification process to described compd A: after completion of the reaction described, the reaction solution of described reaction is standing cooling, use the ethyl acetate washed product, and, 80 ℃ ~ 100 ℃ lower vacuum-dryings 24 hours ~ 48 hours, obtain the described compd A of purifying.
7. the preparation method of gel polymer electrolyte film as claimed in claim 3, it is characterized in that, step (2) also comprises the following purification process to described ionic liquid: after completion of the reaction described, with methylene dichloride or chloroform extraction reaction solution 1 ~ 5 time, collect extraction liquid, strip to using saturated AgNO with deionized water
3aqueous solution titration water by after the organic phase evaporation concentration, and, 80 ℃ ~ 100 ℃ lower vacuum-dryings 24 hours ~ 48 hours, obtains the described ionic liquid of purifying till producing without precipitation.
8. the preparation method of gel polymer electrolyte film as claimed in claim 3, is characterized in that, the matter average molecular weight of described polyvinyl alcohol is 2 ~ 200,000.
9. the preparation method of gel polymer electrolyte film as claimed in claim 3, is characterized in that, described in step (3), organic solvent is acetonitrile, ethanol or tetrahydrofuran (THF), and the mass ratio of described organic solvent and polyvinyl alcohol is 20% ~ 30%.
10. select as described in one as claim 3 ~ 9 purposes of gel polymer electrolyte film in ultracapacitor that method prepares.
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| CN108335922A (en) * | 2018-01-20 | 2018-07-27 | 深圳清华大学研究院 | Dielectric film and preparation method thereof, the capacitor using it |
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| CN113968982A (en) * | 2021-11-01 | 2022-01-25 | Tcl华星光电技术有限公司 | Ionic liquid gel, preparation method thereof and binding method of panel |
Family Cites Families (5)
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| KR100723391B1 (en) * | 2006-01-13 | 2007-05-30 | 삼성에스디아이 주식회사 | Polymer electrolytic membrane , and fuel cell employing the same |
| KR100813242B1 (en) * | 2006-02-14 | 2008-03-13 | 삼성에스디아이 주식회사 | Polymer electrolyte membrane, method for preparing the same and fuel cell using the same |
| US7842637B2 (en) * | 2008-05-23 | 2010-11-30 | Lumimove, Inc. | Electroactivated film with polymer gel electrolyte |
| WO2011019187A2 (en) * | 2009-08-10 | 2011-02-17 | 주식회사 엘지화학 | Lithium secondary battery |
| CN102122704B (en) * | 2010-12-29 | 2013-03-20 | 中科院广州化学有限公司 | Composite microporous membrane used as lithium ion battery diaphragm as well as preparation method and application thereof |
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| CN108335922A (en) * | 2018-01-20 | 2018-07-27 | 深圳清华大学研究院 | Dielectric film and preparation method thereof, the capacitor using it |
| CN113527725A (en) * | 2021-06-26 | 2021-10-22 | 浙江大学衢州研究院 | Preparation method of modified polyvinyl alcohol-based gel electrolyte membrane for lithium-sulfur battery |
| CN113968982A (en) * | 2021-11-01 | 2022-01-25 | Tcl华星光电技术有限公司 | Ionic liquid gel, preparation method thereof and binding method of panel |
| CN113968982B (en) * | 2021-11-01 | 2023-10-31 | Tcl华星光电技术有限公司 | Ionic liquid gel, preparation method thereof and binding method of panel |
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